Composition and process for the controlled synthesis of block copolymers

ABSTRACT

The present invention relates to a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b) at least one hydroxylamine of high molecular weight, preferably a long chain alkyl substituted hydroxylamine. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, and the use of high molecular weight hydroxylamines for controlled polymerization.

This application is a continuation of U.S. application Ser. No.10/568,376, now U.S. Pat. No. 7,572,868, which is a 371 of internationalapp. No. PCT/EP 2004/051817, filed Aug. 18, 2004, the contents of whichare hereby incorporated by reference.

The present invention relates to a polymerizable composition comprisinga) at least one ethylenically unsaturated monomer and b) at least onehydroxylamine, nitrone or alkyl N-oxid of high molecular weight,preferably a long chain alkyl substituted hydroxylamine. Further aspectsof the present invention are a process for polymerizing ethylenicallyunsaturated monomers, and the use of high molecular weighthydroxylamines, nitrones or alkyl N-oxids for controlled polymerization.

Due to the unique properties (appearance, mechanical properties, heatresistance) of vinyl block copolymers with narrow molecular weightdistribution the industrial and technical value of such polymers ishigh. Currently, three methods appear to be most efficient forcontrolled radical polymerization: stable free radical polymerization,best represented by polymerization mediated with tetramethylpiperidine-N-oxyl (TEMPO), metal-catalyzed atom-transfer radicalpolymerization (ATRP) and the reversible addition-fragmentation chaintransfer (RAFT) process. However, all of these methods have certaindisadvantages. The polymerization with TEMPO is relatively slow andTEMPO itself is expensive, the advantages of ATRP are oftenovercompensated by the difficulties of catalyst removal from the polymerand the polymerization with RAFT needs specific dithioesters forspecific monomers and the products are often colored and have anunpleasant odor.

U.S. Pat. No. 6,242,546 and U.S. Pat. No. 6,350,836 therefore suggest asolution to overcome these problems by using hydroxylamines (e.g.dimethylhydroxylamine, diethylhydroxylamine, isopropyl-hydroxylamine,dibenzylhydroxylamine, N-hydroxylmaleimide, N-hydroxylsuccinimide,N-hydroxylphthalimide . . . ), as an easy and inexpensive alternative,for the controlled radical polymerization of vinyl polymers.

The disadvantages of the hydroxylamine derivatives used there are mainlythe high volatility at elevated temperatures, which are necessary forthe polymerization of many vinyl monomers and the missing livingcharacter of the synthesized hydroxylamine terminated polymers i.e. thepossibility to build up block copolymer structures via hydroxylamineterminated macro initiators.

In contrast to low molecular weight hydroxylamines, high molecularweight hydroxylamines, in particular long chain alkyl hydroxylamines,offer the possibility to build up block structures because of theremaining living character of the products of the initial polymerizationstep

The present invention provides the possibility to synthesize blockcopolymer structures by using high molecular weight, in particular longchain alkyl hydroxylamines as controlling agents in the radicalpolymerization of vinyl monomers. Thus radical polymerization of amonomer A followed by a second polymerization step with a monomer B ispossible. The present invention provides a method to obtain di- or eventri-block copolymers respectively, polymer structures, which exhibitinteresting polymer properties due to their defined narrow molecularweight distribution of the individual blocks.

One aspect of the invention is a polymerizable composition comprising

-   -   a) an ethylenically unsaturated monomer;    -   b) a radical polymerization initiator; and    -   c) a hydroxylamine, a nitrone or an alkyl N-oxid having a        molecular weight of more than 250 g/mol.

Preferably the ethylenically unsaturated monomer is selected from thegroup consisting of ethylene, propylene, n-butylene, i-butylene,styrene, substituted styrene, conjugated dienes, acrolein, vinylacetate, vinylpyrrolidone, vinylimidazole, maleic anhydride,(alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylicesters, (alkyl)acrylonitriles, (alkyl)acrylamides, vinyl halides orvinylidene halides.

For example the ethylenically unsaturated monomer is a compound offormula CH₂═C(R_(a))—(C═Z)—R_(b), wherein Z is O or S; R_(a) is hydrogenor C₁-C₄alkyl, R_(b) is NH₂, O⁻(Me⁺), glycidyl, unsubstitutedC₁-C₁₈alkoxy, C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom,or hydroxy-substituted C₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino,di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino orhydroxy-substituted di(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or—O—CH₂—CH₂—N⁺H(CH₃)₂An⁻;

An⁻ is a anion of a monovalent organic or inorganic acid;

Me is a monovalent metal atom or the ammonium ion.

Special preference is given to a polymerizable composition wherein theethylenically unsaturated monomer is styrene, n-butylacrylate,tert-butylacrylate, methylacrylate, ethylacrylate, propylacrylate,hexylacrylate or hydroxyethylacrylate.

Examples of acids from which the anion An⁻ is derived areC₁-C₁₂-carboxylic acids, organic sulfonic acids such as CF₃SO₃H orCH₃SO₃H, mineralic acids such as HCl, HBr or HI, oxo acids such as HClO₄or complex acids such as HPF₆ or HBF₄.

Examples for R_(a) as C₂-C₁₀₀alkoxy interrupted by at least one O atomare of formula

wherein R₁ is C₁-C₂₅alkyl, phenyl or phenyl substituted by C₁-C₁₈alkyl,R_(d) is hydrogen or methyl and v is a number from 1 to 50. Thesemonomers are for example derived from non ionic surfactants byacrylation of the corresponding alkoxylated alcohols or phenols. Therepeating units may be derived from ethylene oxide, propylene oxide ormixtures of both.

Further examples of suitable acrylate or methacrylate monomers are givenbelow.

An⁻, wherein An⁻ and R_(a) have the meaning as defined above and R_(e)is methyl or benzyl. An⁻ is preferably Cl⁻, Br⁻ or ⁻O₃S—CH₃.

Further acrylate monomers are

Examples for suitable monomers other than acrylates are

Preferably R_(a) is hydrogen or methyl, R_(b) is NH₂, gycidyl,unsubstituted or with hydroxy substituted C₁-C₄alkoxy, unsubstitutedC₁-C₄alkylamino, di(C₁-C₄alkyl)amino, hydroxy-substitutedC₁-C₄alkylamino or hydroxy-substituted di(C₁-C₄alkyl)amino; and

Z is oxygen.

More preferred the ethylenically unsaturated monomer is an acrylic acidester, acrylamide, acrylnitrile, methacrylic acid ester, methacrylamide,methacrylnitrile.

Acrylic acid esters and methacrylic acid esters are typicallyC₁-C₁₈alkyl esters.

For example the radical polymerization initiator is a azo compound, aperoxide, a perester or a hydroperoxide.

Preference is given to a polymerizable composition wherein the radicalpolymerization initiator is a azo compound or a peroxide.

Specific preferred radical polymerization initiators are2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methyl-butyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,dimethyl-2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile,2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane),2,2′-azobis(N,N′-dimethyleneisobutyramidine), free base orhydrochloride, 2,2′-azobis(2-amidinopropane), free base orhydrochloride,2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide;acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate,t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate,t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoylperoxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide,bis(2-methylbenzoyl)peroxide, disuccinic acid peroxide, diacetylperoxide, dibenzoyl peroxide, t-butyl per 2-ethylhexanoate,bis-(4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butylpermaleinate, 1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane,1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate,t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butylperacetate, t-amyl perbenzoate, t-butyl perbenzoate,2,2-bis(t-butylperoxy)butane, 2,2 bis (t-butylperoxy)propane, dicumylperoxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy3-phenylphthalide, di-t-amyl peroxide, α,α′-bis(t-butylperoxyisopropyl)benzene, 3,5-bis(t-butylperoxy)3,5-dimethyl 1,2-dioxolane,di-t-butyl peroxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide,3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthanehydroperoxide, pinane hydroperoxide, diisopropylbenzenemono-α-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.

For example in component c) the hydroxylamine, the nitrone or the alkylN-oxid having a molecular weight of more than 250 g/mol are of formulae(I), II) or (III)

whereinR₁, R₂, R₃ and R₄ are independently hydrogen, phenyl or C₁-C₄alkyl;R₅ and R₆ are independently C₇-C₃₅alkyl, C₇-C₃₅alkenyl or C₇-C₃₅alkinyl,which may be unsubstituted or substituted by phenyl, halogen, NH₂,N(R₂₁)₂, —OH, —CN, —NO₂, or —COOR₂₁; or which may be interrupted by —O—or —C(O)—; orR₅ and R₆ together are an alkylene bridge, which may be interrupted by a—O—, —C(O)— or a —N(C₁-C₁₈alkyl)— group to form a heterocyclic 5, 6, 7or 8 membered ring, which may be further substituted by a—O—C(O)—]_(n)R₂₀, NR₂₁—C(O)—]_(n)R₂₀ or a ketal group; n is 1 or 2;wherein, when n is 1, R₂₀ is hydrogen or C₁-C₁₈alkyl and, when n is 2,R₂₀ is C₁-C₁₈alkylene; R₂₁ is hydrogen or C₁-C₁₈alkyl; R₇ and R₈ areindependently C₈-C₃₆alkyl; and R₉ is C₁-C₄alkyl.

For example the hydroxylamine, the nitrone or the alkyl N-oxid has amolecular weight of more than 300 g/mol, for instance more than 350g/mol.

The alkyl radicals in the various substituents may be linear orbranched. Examples of alkyl containing 7 to 35 carbon atoms are methyl,heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl,tridecyl, tetradecyl, hexadecyl, octadecyl and eicosyl.

Alkenyl with 7 to 35 carbon atoms is a linear or branched radical as forexample n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl,n-2-octadecenyl oder n-4-octadecenyl.

Alkinyl with 7 to 35 carbon atoms is a linear or branched radical.

5, 6, 7 or 8 membered heterocyclic rings are for example azepin,piperidine or pyrrolidine.

Examples for hydroxy substituted alkyl are hydroxy propyl, hydroxy butylor hydroxy hexyl.

C₇-C₃₅alkyl interrupted by at least one O atom is for example—(CH₂)₃—CH₂—O—CH₂—CH₃, —(CH₂)₆—CH₂—O—CH₃ or—CH₂—CH₂—O—CH₂—CH₂—CH₂—O—CH₂—CH₃. It is preferably derived frompolyethlene glycol. A general description is —((CH₂)_(a)—O)_(b)—H/CH₃,wherein a is a number from 4 to 10 and b is a number from 2 to 10.

Special preference is given to a polymerizable composition wherein thehydroxylamine is of formula (I).

In one preferred embodiment of the invention the compound of formula (I)is of formula A′, A″, B′ or O′

whereinm is 1,R is hydrogen, C₁-C₁₈alkyl which is uninterrupted or interrupted by oneor more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalentradical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, ofa cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or anα,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of anaromatic carboxylic acid having 7 to 15 carbon atoms;p is 1;R₁₀₁ is C₁-C₁₂alkyl, C₅-C₇cycloalkyl, C₇-C₈aralkyl, C₂-C₁₈alkanoyl,C₃-C₅alkenoyl or benzoyl;R₁₀₂ is C₁-C₁₈alkyl, C₅-C₇cycloalkyl, C₂-C₈alkenyl unsubstituted orsubstituted by a cyano, carbonyl or carbamide group, or is glycidyl, agroup of the formula —CH₂CH(OH)—Z or of the formula —CO—Z or —CONH—Zwherein Z is hydrogen, methyl or phenyl;R₆ and R′₆ together are both hydrogen, a group ═O or ═N—O—R₁₂₀ whereinR₁₂₀ is H, straight or branched C₁-C₁₈alkyl, C₃-C₁₈alkenyl orC₃-C₁₈alkinyl, which may be unsubstituted or substituted, by one or moreOH, C₁-C₈alkoxy, carboxy, C₁-C₈alkoxycarbonyl; C₅-C₁₂cycloalkyl orC₅-C₁₂cycloalkenyl;phenyl, C₇-C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁-C₈alkyl, halogen, OH, C₁-C₈alkoxy,carboxy, C₁-C₈alkoxycarbonyl;—C(O)—C₁-C₃₆alkyl, or an acyl moiety of a α,β-unsaturated carboxylicacid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having7 to 15 carbon atoms;—SO₃ ⁻Q⁺, —PO(O⁻Q⁺)₂, —P(O)(OR₂)₂, —SO₂—R₂, —CO—NH—R₂, —CONH₂, COOR₂, orSi(Me)₃, wherein Q⁺ is H⁺, ammonium or an alkali metal cation; orR₁₀₆ and R′₁₀₆ are independently —O—C₁-C₁₂alkyl, —O—C₃-C₁₂alkenyl,—O—C₃-C₁₂alkinyl, —O—C₅-C₈cycloalkyl, —O-phenyl, —O-naphthyl,—O—C₇-C₉phenylalkyl; orR₁₀₆ and R′₁₀₆ together form one of the bivalent groups—O—C(R₁₂₁)(R₁₂₂)—CH(R₁₂₃)—O—, —O—CH(R₁₂₁)—CH₁₂₂—C(R₁₂₂)(R₁₂₃)—O—,—O—CH(R₁₂₂)—CH₂—C(R₁₂₁)(R₁₂₃)—O—, —O—CH₂—C(R₁₂₁)(R₁₂₂)—CH(R₁₂₃)—O—,—O-o-phenylene-O—, —O-1,2-cyclohexyliden-O—,—O—CH₂—CH═CH—CH₂—O—,

whereinR₁₂₁ is hydrogen, C₁-C₁₂alkyl, COOH, COO—(C₁-C₁₂)alkyl or CH₂OR₁₂₄;R₁₂₂ and R₁₂₃ are independently hydrogen, methyl ethyl, COOH orCOO—(C₁-C₁₂)alkyl;R₁₂₄ is hydrogen, C₁-C₁₂alkyl, benzyl, or a monovalent acyl residuederived from an aliphatic, cycloaliphatic or aromatic monocarboxylicacid having up to 18 carbon atoms;G₆ is hydrogen and G₅ is hydrogen or C₁-C₄alkyl, andG₁, G₂, G₃ and G₄ are methyl; orG₁ and G₃ are methyl and G₂ and G₄ are ethyl or propyl or G₁ and G₂ aremethyl and G₃ and G₄ are ethyl or propyl.C₃-C₁₂cycloalkyl is typically, cyclopropyl, cyclopentyl,methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl ortrimethylcyclohexyl.C₆-C₁₀ aryl is for example phenyl or naphthyl, but also comprised areC₁-C₄alkyl substituted phenyl, C₁-C₄alkoxy substituted phenyl, hydroxy,halogen or nitro substituted phenyl. Examples for alkyl substitutedphenyl are ethylbenzene, toluene, xylene and its isomers, mesitylene orisopropylbenzene. Halogen substituted phenyl is for exampledichlorobenzene or bromotoluene.

Alkoxy substituents are typically methoxy, ethoxy, propoxy or butoxy andtheir corresponding isomers.

C₇-C₉phenylalkyl is benzyl, phenylethyl or phenylpropyl.

C₅-C₁₀heteroaryl is for example pyrrol, pyrazol, imidazol,2,4,dimethylpyrrol, 1-methylpyrrol, thiophene, furane, furfural, indol,cumarone, oxazol, thiazol, isoxazol, isothiazol, triazol, pyridine,α-picoline, pyridazine, pyrazine or pyrimidine.

If R is a monovalent radical of a carboxylic acid, it is, for example,an acetyl, propionyl, butyryl, valeroyl, caproyl, stearoyl, lauroyl,acryloyl, methacryloyl, benzoyl, cinnamoyl orβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.

C₁-C₁₈alkanoyl is for example, formyl, propionyl, butyryl, octanoyl,dodecanoyl but preferably acetyl and C₃-C₅alkenoyl is in particularacryloyl.

The above compounds and their preparation are described in GB 2335190and in WO 02/48205.

A suitable compound is for example

In another preferred embodiment of the invention in the hydroxylamine offormula (I) R₁, R₂, R₃ and R₄ are hydrogen; and R₅ and R₆ independentlyare C₇-C₃₅alkyl or C₇-C₃₅alkenyl.

The above open chain hydroxylamines can be prepared according tostandard methods and are largely items of commerce.

A further aspect of the invention is a process for preparing anoligomer, a cooligomer, a polymer or a copolymer (block, random orgraft) by free radical polymerization of at least one ethylenicallyunsaturated monomer or oligomer, which comprises (co)polymerizing themonomer or monomers/oligomers in the presence of

-   -   b) a free radical initiator and    -   c) a hydroxylamine, a nitrone or an alkyl N-oxid having a        molecular weight of more than 250 g/mol.

After the polymerization step is completed the reaction mixture may becooled down to a temperature below 60° C., preferably to roomtemperature. The polymer may be stored at this temperature withoutfurther reactions occurring.

The process may be carried out in the presence of an organic solvent orin the presence of water or in mixtures of organic solvents and water.Additional cosolvents or surfactants, such as glycols or ammonium saltsof fatty acids, may be present. Other suitable cosolvents are describedhereinafter.

When acrylic or methacrylic monomers are polymerized, the process ispreferably carried out in the presence of an organic solvent. Theconcentration of the monomer in the organic solvent may influencepolymerization rate and final conversion. The concentration may, forexample, vary from 5% to 80% by weight, based on the solvent. It is notnecessary that the whole amount of monomer is present at the beginningof the polymerization. It is also possible to add further monomer afterthe polymerization reaction has already started.

If organic solvents are used, suitable solvents or mixtures of solventsare typically pure alkanes (hexane, heptane, octane, isooctane),aromatic hydrocarbons (toluene, xylene), halogenated hydrocarbons(chlorobenzene), alkanols (methanol, ethanol, ethylene glycol, ethyleneglycol monomethyl ether), esters (ethyl acetate, propyl, butyl or hexylacetate) and ethers (diethyl ether, dibutyl ether, ethylene glycoldimethyl ether), or mixtures thereof.

The aqueous polymerization reactions can be supplemented with awater-miscible or hydrophilic cosolvent to help ensure that the reactionmixture remains a homogeneous single phase throughout the monomerconversion. Any water-soluble or water-miscible cosolvent may be used,as long as the aqueous solvent medium is effective in providing asolvent system which prevents precipitation or phase separation of thereactants or polymer products until after all polymerization reactionshave been completed. Exemplary cosolvents useful in the presentinvention may be selected from the group consisting of aliphaticalcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkylpyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols,polypropylene glycols, amides, carboxylic acids and salts thereof,esters, organosulfides, sulfoxides, sulfones, alcohol derivatives,hydroxyether derivatives such as butyl carbitol or cellosolve, aminoalcohols, ketones, and the like, as well as derivatives thereof andmixtures thereof. Specific examples include methanol, ethanol, propanol,dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol,dipropylene glycol, tetrahydrofuran, and other water-soluble orwater-miscible materials, and mixtures thereof. When mixtures of waterand water-soluble or water-miscible organic liquids are selected as theaqueous reaction media, the water to cosolvent weight ratio is typicallyin the range of about 100:0 to about 10:90.

The process is particularly useful for the preparation of blockcopolymers.

Block copolymers are, for example, block copolymers of polystyrene andpolyacrylate (e.g., poly(styrene-co-acrylate) orpoly(styrene-co-acrylate-co-styrene). They are useful as adhesives or ascompatibilizers for polymer blends or as polymer toughening agents.Poly(methylmethacrylate-co-acrylate) diblock copolymers orpoly(methylacrylate-co-acrylate-co-methacrylate) triblock copolymers)are useful as dispersing agents for coating system, as coating additives(e.g. rheological agents, compatibilizers, reactive diluents) or asresin component in coatings (e.g. high solid paints). Block copolymersof styrene, (meth)acrylates and/or acrylonitrile are useful as forshaping plastic articles and as modifiers for plastics, elastomers andadhesives.

Furthermore, block copolymers of this invention, wherein the blocksalternate between polar monomers and non-polar monomers, are useful inmany applications as amphiphilic surfactants or dispersants forpreparing highly uniform polymer blends.

The (co)polymers of the present invention may have a number averagemolecular weight from 1 000 to 400 000 g/mol, preferably from 2 000 to250 000 g/mol and, more preferably, from 2 000 to 200 000 g/mol. Thenumber average molecular weight may be determined by size exclusionchromatography (SEC), matrix assisted laser desorption/ionization massspectrometry (MALDI-MS) or, if the initiator carries a group which canbe easily distinguished from the monomer(s), by NMR spectroscopy orother conventional methods.

For instance the polymer obtained has a polydispersity of between 1.1and 2.5, for example between 1.3 and 2.1.

In principal the polymerization can be carried out by heating orexposure to electromagnetic radiation, ranging from γ to microwaves.

Preferably the polymerization is carried out by heating and takes placeat a temperature of between 50° C. and 160° C., preferably between 70°C. and 160° C.

Preferably the hydroxylamine, the nitrone or the alkyl N-oxid having amolecular weight of more than 250 is present in an amount of 0.001 to 10mol %, in particular of 0.1 to 5 mol % based on the monomer or monomers.

If a mixture of monomers is used, mol % is based on an average molecularweight of the monomers.

The radical polymerization initiator is, for example, present in anamount from 0.002 to 5% by weight, based on the weight of the monomer ormonomers.

For instance the weight ratio between the radical polymerizationinitiator and the hydroxylamine, the nitrone or the alkyl N-oxid havinga molecular weight of more than 250 g/mol is from 1:5 to 5:1.

Thus, the present invention also encompasses in the synthesis novelblock, multi-block, star, gradient, random, hyperbranched and dendriticcopolymers, as well as graft copolymers.

The polymers prepared by the present invention are useful for followingapplications: adhesives, detergents, dispersants, emulsifiers,surfactants, defoamers, adhesion promoters, corrosion inhibitors,viscosity improvers, lubricants, rheology modifiers, thickeners,crosslinkers, paper treatment, water treatment, electronic materials,paints, coatings, photography, ink materials, imaging materials,superabsorbants, cosmetics, hair products, preservatives, biocidematerials or modifiers for asphalt, leather, textiles, ceramics andwood.

Further aspects of the invention are a polymer or copolymer obtainableby a process as outlined above and the use of a hydroxylamine, a nitroneor an alkyl N-oxid having a molecular weight of more than 250 for thecontrolled polymerization of ethylenically unsaturated monomers.

Definitions and preferences for the individual components have alreadybeen given. They apply also to the other aspects of the invention.

The following examples illustrate the invention.

-   Compound 101: N,N,-Dioctadecyl-hydroxylamine from Fluka.-   Compound 102:

where R₁═C₁₈ and R₂═C₁₇ from Fluka.

-   Compound 103: Genox EP® from General Electric Speciality Chemicals,    Inc. (bis(hydrogenated rape-oil alkyl)methyl,N,oxide)-   Comparative compound: N,N Diethylhydroxylamine from Merck KGaA,    Darmstadt, Germany    Standard Polymerization Procedure:

In a dry, argon-purged Schlenk tube, the given amounts of hydroxylaminederivative and radical initiator are dissolved in 0.5 mol freshlydistilled styrene. The solution is degassed in three consecutivefreeze-thaw-cycles and than purged with argon. The stirredmixture/solution is then immersed in an oil bath and polymerized at 130°C. for 24 h. After polymerization, residual monomer is removed,respectively the polymer is dried under vacuum at 50° C. until aconstant weight is achieved. 2.5 g of the in this way obtained macroinitiator are dissolved in 15 g n-butyl acrylate and again polymerizedfor 6 h in the previously described manner.

Hydroxylamines were used as received.

Dibenzoyl peroxide (BPO) (Merck) was recrystallized from Methanol priorto use.

Styrene was distilled under reduced pressure prior to use.

Test Procedures:

Molecular weight and molecular weight distributions are determined byGPC on a HP 1090 liquid chromatograph (software: winGPC/Polymer StandardServices, Mainz, Germany) using THF as eluent and a column combinationcalibrated with narrow molecular weight polystyrene standards (PolymerLaboratories).

Styrene polymerization is carried out with the compositions presented inTable 1 at 130° C. for 24 h according to the above standard procedure.

TABLE 1 Comparative Comp Comp. Comp. Compound 101 103 102 BPO No [mol %][mol %] [mol %] [mol %] [mol %] Comparative ex. 1 0.05 0.1 Comparativeex. 2 0.1 0.1 Comparative ex. 3 0.15 0.1 Comparative ex. 4 0.2 0.1Inventive ex. 1 0.05 0.1 Inventive ex. 2 0.1 0.1 Inventive ex. 3 0.150.1 Inventive ex. 4 0.2 0.1 Inventive ex. 5 0.05 0.1 Inventive ex. 6 0.10.1 Inventive ex. 7 0.15 0.1 Inventive ex. 8 0.2 0.1 Inventive ex. 90.05 0.1 Inventive ex. 10 0.1 0.1 Inventive ex. 11 0.15 0.1 Inventiveex. 12 0.2 0.1

The macro initiators obtained were dried, then dissolved in n-butylacrylate and polymerized at 130° C. for 6 h.

The conversions and polydispersities of the styrene-n-butylacrylateco-polymers obtained by the controlled radical polymerization of styrenefollowed by a reinitaition reaction of the obtained macroinitiators withn-butyl acrylate are summarized in Table 2.

Mn_crp symbolizes the average molecular weight of the styrenic macroinitiator, Mn_reini the molecular weight of the block co-polymer, at theend of the reinitiation reaction. A positive value for Mn_reini minusMn_crp is equal to the building up of a block structure a negative valuedemonstrates the decomposition of the macro initiator.

TABLE 2 Conversion- Mn_reini − Polydisp. crp Mn_crp Mn_reini Mn_crpafter No [%] [g/mol] [g/mol] [g/mol] reinitiation Comparative ex. 1 96.096700 80000 −16700 2.8 Comparative ex. 2 92.7 131000 90000 −41000 2.2Comparative ex. 3 91.0 118000 75500 −42500 2.8 Comparative ex. 4 88.2142000 100100 −41900 2.1 Inventive ex. 1 97.9 138500 201100 62600 2.3Inventive ex. 2 88.5 131800 134700 2900 1.8 Inventive ex. 3 73.1 120500169700 49200 1.8 Inventive ex. 4 63.4 85080 115100 30020 1.9 Inventiveex. 5 85.9 146400 198900 52500 2.7 Inventive ex. 6 84.3 139100 15300013900 2.1 Inventive ex. 7 82.4 109600 168700 59100 2.3 Inventive ex. 878.8 98600 144700 46100 2.3 Inventive ex. 9 99.0 136400 180500 44100 2.5Inventive ex. 10 96.8 118000 185900 67900 2.6 Inventive ex. 11 98.0116600 158200 41600 2.4 Inventive ex. 12 95.5 108000 165300 57300 2.3

Table 2 illustrates that a controlled free radical polymerization ispossible with the short alkyl chain N,N diethyl-hydroxylamine as well aswith the long alkyl chain compound 101, N,N dioctadecyl-hydroxylamineand also with the corresponding Nitrone, compound 103 (Genox EP) ormethyl, N-oxide, compound 102. However, Table 2 also clearly shows thatbuilding up of a block structure is only possible for the inventiveexamples, indicated by the positive value of Mn_reini minus Mn_crp. Themacro initiators obtained by the polymerization of styrene in thepresence of N,N Diethyl-hydroxylamine (comparative examples) decomposeunder the conditions of the butylacrylate polymerization and blockstructures cannot be obtained.

1. A polymerizable composition comprising a) an ethylenicallyunsaturated monomer; b) a radical polymerization initiator; and c)N,N-dioctadecylhydroxylamine.
 2. A polymerizable composition accordingto claim 1 wherein the ethylenically unsaturated monomer is selectedfrom the group consisting of ethylene, propylene, n-butylene,i-butylene, styrene, substituted styrene, conjugated dienes, acrolein,vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride,(alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylicesters, (alkyl)acrylo-nitriles, (alkyl)acrylamides, vinyl halides andvinylidene halides.
 3. A polymerizable composition according to claim 1wherein the ethylenically unsaturated monomer is a compound of formulaCH₂═C(R_(a))—(C═Z)—R_(b), wherein Z is O or S; R_(a) is hydrogen orC₁-C₄alkyl; R_(b) is NH₂, O⁻(Me⁺), glycidyl, unsubstituted C₁-C₁₈alkoxy,C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom, orhydroxy-substituted C₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino,di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino orhydroxy-substituted di(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or—O—CH₂—CH₂—N⁺H(CH₃)₂ An⁻; An⁻ is a anion of a monovalent organic orinorganic acid; and Me is a monovalent metal atom or the ammonium ion.4. A polymerizable composition according to claim 2 wherein theethylenically unsaturated monomer is styrene, n-butylacrylate,tert-butylacrylate, methylacrylate, ethylacrylate, propylacrylate,hexylacrylate or hydroxyethylacrylate.
 5. A polymerizable compositionaccording to claim 1 wherein the radical polymerization initiator is aazo compound, a peroxide, a perester or a hydroperoxide.
 6. Apolymerizable composition according to claim 5 wherein the radicalpolymerization initiator is a azo compound or a peroxide.